559588 A7 B7 五、發明說明(1) 本發明係有關用於隱形眼鏡製造之模具及模具嵌件。 尤其’本發明提供用於製造矽氧烷水凝膠隱形眼鏡之高光 學品質的模具及模具嵌件。 為美容及校正視覺敏銳度之理由而使用軟性隱形眼鏡為 屬已知。基本上,此等隱形眼鏡係藉鑄造來製造。於鏡片 鑄造中所使用之模具半模係先藉切削加工金屬嵌件,然後 使用嵌件製造模具半模。切削嵌件的過程可能會引起週期 性缺陷或週期性結構,其可被轉移至模具半模中。模具半 模的模塑表面適合在模具半模中製造傳統水凝膠鏡片鑄件 之光學品質鏡片。 經 濟 部 智 慧 財 產 局 員 工 消 t 合 作 社 印 製 然而,在矽氧烷水凝膠鏡片的鑄造成形中,矽氧烷水凝 膠材料精密地複製模具表面。因此,模具表面上之週期性 結構被轉移至鏡片表面。若鏡片被塗覆有可膨脹,或親水 性塗料,則塗料的膨脹會擴大此等表面缺陷。這些擴大的 缺陷可能會因產生干涉散射(分光作用)或眼睛保健專業 人員可見的切削痕跡而危及鏡片穿戴者之視覺。於是,模 具可能製造出具低於光學品質表面之經塗覆之矽氧烷水凝 膠鏡片。因此,亟需要一種方法及材料來克服此問題。 螢明說明及其之幹传具體例 本發明提供用於鑄造成形矽氧烷水凝膠隱形眼鏡之模 具、製造模具之嵌件及利用本發明之模具所製得之鏡片。 -3- 張尺度適用中Η國^準(CNS)A4規格(210 X 297公釐)一- 559588 A7559588 A7 B7 V. Description of the invention (1) The present invention relates to a mold and a mold insert for contact lens manufacturing. In particular, the present invention provides molds and mold inserts of high optical quality for making silicone hydrogel contact lenses. The use of soft contact lenses for reasons of beauty and correction of visual acuity is known. Basically, these contact lenses are manufactured by casting. The mold halves used in lens casting are first processed by cutting metal inserts, and then the inserts are used to make the mold halves. The process of cutting inserts can cause periodic defects or periodic structures that can be transferred to the mold half. The mold surface of the mold half is suitable for making optical quality lenses of traditional hydrogel lens castings in the mold half. Printed by the Intellectual Property Office of the Ministry of Economic Affairs and Consumer Affairs Co., Ltd. However, in the casting of the silicone hydrogel lens, the silicone hydrogel material accurately replicates the surface of the mold. Therefore, the periodic structure on the mold surface is transferred to the lens surface. If the lens is coated with an expandable, or hydrophilic coating, the expansion of the coating can amplify these surface defects. These enlarged defects can endanger the vision of the lens wearer due to interference scattering (spectroscopy) or cutting marks visible to eye care professionals. Thus, it is possible for the mold to produce a coated silicone hydrogel lens with a surface that is less than optical quality. Therefore, a method and materials are urgently needed to overcome this problem. Description of the fluorescence and specific examples of dry transmission The present invention provides a mold for casting and forming a silicone hydrogel contact lens, an insert for manufacturing a mold, and a lens made by using the mold of the present invention. -3- Zhang scale applies to China Laos Standard (CNS) A4 (210 X 297 mm) 1-559588 A7
本發明之模具具有模塑表面,其上之·結構(由形成模 具之欲件的切削加工所產生)為由輻角及週期性所構成, 會比當鏡諸塗覆_導致鏡絲面產生鱗穿戴者視覺 之光學缺陷者要少。 於-具體例中,本發明提供一種鏡片嵌件,其包括、 實質上包含及包含至少—種光學臨界表面,其中在光學臨 界表面上之週期結構為低於約3微米之週期性和低於約4 奈米RMS之幅角。在另―具制巾,本發明提供用於製 造模塑隱形眼鏡之半模,該半模包括、實質包含及包含至 少-種模塑表面’其中在模塑表面上之週期結構為低於約 3微米之週期性和低於約4奈米RMS之幅角。在又一具 體例中,本發明提供矽氧烷水凝膠隱形眼鏡,其包括、實 質包含及包含至少-種表面,其中在表面上之週期結構為 低於約3微米之週期性和低於約4奈米RMS之幅角。為 本發明之目的,幅角的測定係利用原子力顯微鏡在5〇χ5〇 微米之面積上進行。 經濟部智慧財產局員工消費合作社印製 所谓光學臨界表面”意表製造鏡片模具或半模之模塑表 面用之模具嵌件的表面。所謂“模塑表面,,意表用來形成鏡 片表面之模具或半模之表面。 本發明嵌件之光學臨界表面較佳被拋光,使表面結構 不規則分布形成並降低粗糙度至所期望的程度。嵌件先藉 任何適合的方法,包括(但非限制)藉適當材料之單一金 鋼石尖頭旋轉法。基本上,嵌件係利用一控制波紋之金鋼 石切削刀具,以至多兩次利用相同工具潤飾切割予以成 -4- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 559588 A7 B7 五、發明說明(3) 形。一般熟悉該項技術者將知曉控制波紋之刀具為一種刀 具,其不管在刀具之切割部分的那一點上做切割,在該點 上之半徑為經刀具標記予以規袼化,在容許極限内,僅有 最小的局部偏差。此一刀具提供最終部分切割將是極度精 確的。刀具刀尖半徑約100至250微米的範圍。 嵌件拋光以提供本發明之光學臨界表面者可藉任何適 合的方法實施。較佳地,拋光係利用一被塗覆至布上之重 碳金鋼石拋光化合物和被成形以配合嵌件半徑之鑽模來實 施。將嵌件及鑽模置於拋光機中一段適當時間,例如約j 分鐘,然後以一適當之溶劑(如一種醇)去除並擦拭,以 去除拋光化合物。然後審視嵌件並視需要重覆該過程。嵌 件最後藉任何適合的方法,包括(非限制)使用干涉儀加 以審視,以確定半徑符合設計規格及週期結構為所期望之 週期性及幅角。 經濟部智慧財產局員工消費合作社印製 作為拋光之替代方法可選擇使用適合製造本發明光學 臨界表面之條件的車床,使週期結構之幅角及週期性為在 所期望之範圍内。例如,使用直線進給速率或金鋼石刀具 沿著零件表面定軌跡的速度(以毫米/分鐘測量)對主轴 轉速(轉/分鐘)的比例,其足以提供各車床線或螺旋之 間所欲之增量。為獲得1微米間隔之車床線,吾人使用5 毫米/分鐘直線進給和5000 rpm、1〇毫米/分鐘直線進 給和10000 rpm或任何提供1/1000比例之數字。為獲得 低於300奈米間隔之車床線,所使用之適當比例為 3/10000,或2.4毫米/分鐘之直線進給和8〇〇〇 rpm之主 -5- 559588The mold of the present invention has a molding surface, and the structure thereon (produced by the cutting process of forming a desired part of the mold) is composed of an angle and a periodicity, which will cause the mirror silk surface to be produced more than when the mirror is coated. Scale wearers have fewer optical defects. In a specific example, the present invention provides a lens insert including, substantially including, and including at least one optically critical surface, wherein the periodic structure on the optically critical surface has a periodicity of less than about 3 microns and a periodicity of less than about 3 microns. Angle of about 4 nm RMS. In another aspect, the present invention provides a mold half for manufacturing a molded contact lens, the mold half including, substantially containing, and including at least one molding surface, wherein the periodic structure on the molding surface is less than about A periodicity of 3 microns and an amplitude angle below about 4 nm RMS. In yet another specific example, the present invention provides a silicone hydrogel contact lens comprising, substantially including, and including at least one surface, wherein the periodic structure on the surface is less than about 3 microns in periodicity and less than about 3 microns. An angle of about 4 nm RMS. For the purposes of the present invention, the measurement of the angle is performed using an atomic force microscope over an area of 50 x 50 microns. The printing of the so-called optical critical surface by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs intends to manufacture the surface of the mold insert used to mold the lens mold or the mold surface of the half mold. The surface of the half mold. The optical critical surface of the insert of the present invention is preferably polished, so that the surface structure is irregularly distributed and the roughness is reduced to a desired degree. The insert is first borrowed by any suitable method, including (but not limited to) a single diamond tip rotation method of suitable material. Basically, inserts are made with a diamond-cutting tool that controls corrugations, and trimmed and cut with the same tool up to two times. -4- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). 559588 A7 B7 V. Description of the invention (3) Shape. Those skilled in the art will generally know that the tool for controlling the corrugation is a kind of tool, regardless of the point where the cutting part of the tool is cut, the radius at this point is regulated by the tool mark, within the allowable limit, There is only minimal local deviation. This tool will be extremely precise in providing the final partial cut. The tool tip radius ranges from about 100 to 250 microns. The polishing of the insert to provide the optically critical surface of the present invention can be performed by any suitable method. Preferably, the polishing is performed using a heavy carbon diamond polishing compound applied to the cloth and a drill die shaped to fit the radius of the insert. The insert and the die are placed in a polishing machine for a suitable period of time, such as about j minutes, and then removed and wiped with a suitable solvent (such as an alcohol) to remove the polishing compound. Then review the insert and repeat the process as necessary. The insert finally uses any suitable method, including (non-restrictive) inspection with an interferometer to determine that the radius meets the design specifications and the periodic structure is the desired periodicity and angle. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. As an alternative to polishing, a lathe suitable for the conditions for manufacturing the optical critical surface of the present invention may be used so that the amplitude and periodicity of the periodic structure are within the desired range. For example, the ratio of the linear feed rate or the speed of a diamond tool's trajectory along the part surface (measured in millimeters per minute) to the spindle speed (revolutions per minute) is sufficient to provide the desired between the lathe lines or spirals In increments. To get a 1 micron interval lathe line, we use 5 mm / min linear feed and 5000 rpm, 10 mm / min linear feed and 10000 rpm or any number that provides a 1/1000 ratio. In order to obtain a lathe line with an interval of less than 300 nanometers, the appropriate ratio used is 3/10000, or a linear feed of 2.4 mm / min and a master of 8000 rpm -5- 559588
轴轉速。 本發明之嵌件可由任何可做光學加工之材料所構成,包 括(非限制)金屬、石英、陶瓷、聚合物等。適合之金屬 包括(非限制)純鋼、黃銅、銅、鍍鎳基材、鉻、鈷_錄 合金之馬丁散鐵鋼、AMPCOLOY™基材等及彼等之組合 物。較佳地,嵌件為鍍鎳銅或鍍鎳黃銅。有用之聚合物材 料的實例包括(非限制)聚碳酸醋、環稀、耐隆、 DELRIN®、TEFLON®、聚苯乙烯、聚丙烯、聚(丙烯腈) 等及其組合物。 嵌件利用任何習知方法被用來形成本發明之模具或半 模。通常,模具係由嵌件所鑄造。基本上,適合供形成模 具或半模之模塑表面之嵌件應與被用來形成模具或半模之 非-模塑表面之互補嵌件成一對。本發明之模具可由任何 適合供用於隱形眼鏡製造之材料所製成。適合之模具材料 包括(非限制)聚烯類,如聚丙烯、聚苯乙烯及環狀聚 烯、聚丙烯腈材料等及其組合物。 經濟部智慧財產局員工消費合作社印製 本發明之模具及彼件可用來製造任何種類之碎氧烧水凝 膠鏡片。本發明之鏡片為矽氧烷水凝膠,較佳矽氧烷水凝 膠被塗覆一層可膨脹塗料。適合之矽氧烷水凝膠材料包括 (非限制)由矽巨體所製得之矽氧烷水凝膠,諸如描述於 美國專利案43259,467、4,260,725及4,261,875中之以懸 垂之親水基團予以甲基丙烯酸酯化之聚二甲基矽氧烷;或 描述於美國專利案 4,136,250; 4,153,641; 4,189,546; 4,182,822; 4,343,927; 4,254,248; 4,355,147; 4,276,402; 4,327,203; 4,341,889; -6· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公爱) 559588 Α7 Β7 五、發明說明(5) 4,486,577; 4,605,712; 4,543,398; 4,661,575; 4,703,097; 4,837,289; 4,954,586; 4,954,587; 5,346,946; 5,358,995; 5,387,632; 5,4513617; 5,486,579; 5,962,548; 5,981,615; 5,981,675 及 6,039,913 中之具可 聚合官能性之聚二甲基矽氧烷巨體。彼等亦可利用組合有 親水性單體之聚矽氧烷巨體予以製造,如描述於美國專利 案 5,010,141; 5,057,578; 5,314,960; 5,371,147 及 5,336,797 中者;或包含聚二甲基矽氧烷嵌段物及聚醚嵌段物之巨 體,如描述於美國專利案4,871,785及5,034,461中者。 所述專利案之全部内容全併入本文作為參考。 適合之材料亦可由oxyperm及ionoperm成分之組合物 所製造,諸如描述於美國專利案5,760,100; 5,776,999; 5,789,461; 5,807,944; 5,965,631 及 5,958,440。親水性單體 經濟部智慧財產局員工消費合作社印製 可混入此等共聚物中,包括2-羥基乙基甲基丙烯酸酯、孓 經基乙基丙稀酸酯(“HEMA”)、N,N-二甲基丙稀醯胺 (DMA”)、N-乙烯0比洛唆_、2-乙烯·4,4’·二甲基-2-今唾 唯-5-酮、甲基丙烯酸、2_羥基乙基甲基丙烯醯胺。可加 入其他矽氧烷單體,如三(三甲基矽氧)甲矽基丙基甲基丙 烯酸酯,或描述於美國專利案5998 498; 3,8〇8178; 4,139,513; 5,070,215; 5,710,302; 5,714,557 和 5,908,906 中 之矽氧烷單體。彼等亦可包括各種韌化劑、調色劑、υν 阻斷劑及濕潤劑。彼等可利用稀釋劑,如描述於美國專利 案6,020,445中之一級醇或二級醇或第三醇來製造。所述 專利案之全部内容全併入本文作為參考。 在較佳具體财,本發明之鏡片係將—種巨體與包 -7- 559588 A7 B7 五、發明說明(6) 單體和親水性單體為底之矽氧烷的反應混合物進行反應所 製得。巨體可藉於一種基團轉移聚合(“GTP”)催化劑的存 在下組合一種甲基丙烯酸酯或一種丙烯酸酯與矽氧烷所製 造。此等巨體基本上為各種單體之共聚物。彼等之形成可 為單體成明顯嵌段或成一般隨機分佈的形式聚集。此等巨 體可進一步為直線、分支或星狀形式。分支結構之形成例 如若聚甲基丙烯酸酯或可交聯單體(如3-(三甲基梦氧基) 丙基甲基丙烯酸酯)被含括於巨體中者。 可用來製造GTP聚合物之引發劑、反應條件、單體及 催化劑被描述於O.W· Webster於聚合物科學及工程百科 經濟部智慧財產局員工消費合作社印製 (John Wiley & Sons)第580頁(1987)中所述之“基團_轉移 聚合法”中。此等聚合反應係在無水條件下進行。經基官 能性單體(像HEMA)可被混入成為彼等之三甲基梦氧 酯,於聚合後以水解形成自由羥基。GTP提供聚集具控 制分子量分佈及於鏈上之單體分佈之巨體的能力。然後此 巨趙可與主要為聚二甲基矽氧烧(較佳為單甲基丙烯氧基 丙基封端之聚二甲基矽氧烷(“mPDMS”))和親水性單體之 反應混合物。較佳之mPDMS為式: ^59 个59 〒59 ^58一Si—O-^· Si-Si-1^〇 R59 R59 R59 其中b=G至⑽,較佳8至1G ; R58為包含乙婦不飽和部 分之單價基81,較佳為包含苯乙縣、㈣基或甲基丙稀 酸酯基部分,尤佳為甲基丙烯酸酯基部分之單價基團·各 R59獨立地為單價烷基、或芳基,其可進一步經醇、胺、 -8 - 559588 A7 B7 五、發明說明(7) _、羧酸或醚基所取代,較佳為未經取代之單價烷基或芳 基,尤佳為甲基;及尺6〇為單價烷基、或芳基,其可進一 步經醇、胺、酮、羧酸或醚基所取代,較佳為未經取代之 單價烷基或芳基,較佳為C^o脂族或芳香族基(其可包 括雜原子),尤佳為C3_8烷基,最佳為丁基,特佳為第二 丁基。 經濟部智慧財產局員Η消費合作社印製 較佳之巨體成分包括mPDMS、3-甲基丙烯氧基丙基三 (三甲基矽氧基)矽烷(“TRIS”)、甲基丙烯酸甲酯、 HEMA、DMA、甲基丙烯腈、甲基丙烯酸乙酯、甲基丙 烯酸丁酯、2-羥基丙基-1-曱基丙烯酸酯、2-羥乙基甲基丙 烯酸酯及甲基丙烯酸。甚至更佳者,巨體係由HEMA、 甲基丙烯酸甲酯、TRIS及mPDMS之反應混合物所製 得。最佳者,巨體係由包括、實質上包含或包含約19.1 莫耳之HEMA、約2·8莫耳之甲基丙烯酸甲酯、約7.9莫 耳之TRIS及約3.3莫耳之單甲基丙烯氧基丙基封端之單 丁基封端之聚二甲基矽氧烷之反應混合物所製得,並藉將 上述材料與每莫耳約2.0莫耳之3-異丙烯基-ω,ω-二甲基 苄基異氰酸酯反應,利用二月桂酸二丁錫為催化劑而完 成。 矽氧烷水凝膠之反應成分基本上為疏水性矽氡烷與極 親水性之成分的組合物。因為此等成分由於彼等極性上之 差異通常不互溶,所以特別有利於將一種疏水性矽氧烧單 體與親水性單體(特別是那些具羥基者)之組合物組合成 為巨體。此巨體隨後用來與混入最終反應混合物中之其他 -9- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) A7 B7 559588 五、發明說明(0 矽氧烷及親水性單體相容。此等摻合物典型亦包含稀釋劑 以進一步相容及溶解所有的成分。較佳地,以石夕氧烧為底 之水凝膠係藉反應下列單體混合物所製成:巨體;si7-9單 甲基丙烯氧基封端之聚二甲基矽氧烷;及親水性單體併同 小量之添加物和光引發劑。尤佳地,水凝膠係藉反應下列 單體所製成:Si7_9單甲基丙烯氧基封端之聚二甲基矽氧 烷;TRIS ; DMA ; HEMA及四乙二醇二甲基丙烯酸酯 (“TEGDMA”)。最佳地,水凝膠係由巨體(約18%) ; Si7_9 單甲基丙烯氧基封端之聚二甲基矽氧烷(約28%); DMA (約 26%) ; HEMA(約 5%) ; TEGDMA(約 1%);聚乙烯吡 咯啶酮(“PVP”)(約5%)及包含小量添加物和光引發劑之餘 • 量(所有的用量係以組合物之總重量之重量百分比來計 算)之反應所製得,該反應係在20重量%之二甲基-3·辛 醇稀釋劑的存在下進行。 經濟部智慧財產局員工消費合作社印製 隱形眼鏡表面可藉諸如塗覆適當親水性塗料的任何便利 方法予以塗覆一可膨脹塗層。此塗料可藉任何便利的方法 予以塗覆。較佳之親水性塗料包括(非限制)聚(丙烯 酸)、聚(甲基丙烯酸)、聚(順丁烯二酸)、聚(衣康酸)、聚 (丙烯醯胺)、聚(一甲基丙婦醯胺)、(甲基)丙婦酸、丙稀 酸、(順丁烯二酸、衣康酸與任何反應性乙烯單體、羧甲 基化之聚合物,諸如羧甲基纖維素、糊精、聚乙烯醇、聚 環氧乙烷、聚(HEMA)、聚磺酸酯、聚硫酸酯、聚内醯 胺、聚乙醇酸、聚胺等及其混合物,之嵌段或無規共聚 物。尤佳地’塗料為聚(丙烯酸)、聚(甲基丙烯酸)、聚 -10- 559588 A7 B7 五、發明說明(9) 甲基)丙烯醯胺、聚(丙烯醯胺)或聚(HEMA)。最佳係使用 聚(丙烯酸)、聚(丙稀醯胺)或聚(HEMA)。 本發明之鏡片可利用任何供隱形眼鏡製造用之習知方法 來製造。較佳地,鏡片係藉光固化鏡片組成物並塗覆一層 塗料至經固化的鏡片上來製造。在隱形眼鏡製造上各種已 知可供模塑反應混合物的方法包括旋轉鑄造及靜態澆注。 製造本發明隱形眼鏡之較佳方法為藉矽氧烷水凝膠之直接 模塑法,其為經濟的,且能精確控制水合鏡片之最終形狀 。就此方法而言’係將反應混合物置於具有最終所欲梦氧 烷水凝膠(即水膨脹聚合物)之形狀的模具中,並使反應 混合物接受單體可聚合之條件,以製造有最終所欲產物之 近似形狀之聚合物。此種聚合反應之條件為此技藝中所熟 知的。聚合物混合物視情況可經溶劑然後用水處理,產生 一種具有最終大小及形狀類似原始模塑之聚合物物品之大 小及形狀之石夕氧烧水凝膠。此方法可用來形成隱形眼鏡且 此方法進一步被描述於美國專利案4,495,313,4,680,33ό 4,889,664及5,039,459中(彼等全部併入本文作為參 考)。 經濟部智慧財產局員工消費合作社印製 本發明將藉由考慮下列非限制性實施例進一步予以閣明 〇 實施例1-18 嵌件及模具製造 嵌件係由黃銅藉金鋼石尖頭翻轉法,利用一控制波紋之 -11- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)^------ 559588 A7 B7 五、發明說明(10) 刀具尖頭來製造。除非另有指明,否則所有的黃銅嵌件都 以4次半完成之切削予以切割,切割深度= 0.25毫米, 主轴轉速8,000 rpm及進給速率25毫米/分鐘。然後切 割嵌件,切割深度= 0.005毫米,8,000 rpm之主軸轉速及 5毫米/分鐘之進給速率。然後嵌件為:1.)未處理;2.)以 約2-4微米之薄鎳塗料處理,藉蒸發被塗覆至嵌件表面; 3·)以約100-200微米之薄鎳塗料處理,藉蒸發被塗覆至嵌 件表面;或4·)利用金鋼石拋光膏予以拋光。 實施例1-18,鏡片模具半模利用下表中所列之嵌件由 TOP AS聚合物予以射出成形。將散件安裝於8穴射出成 形機中並將熔化之TOPAS®,在約290-300°C下,於壓力 下注入模具中。釋放壓力,使模具冷卻,開啟及將模彈 出。 鏡片形成-實施例M8 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 製造鏡片所用之巨體係藉於14t:下,於氮氣氛圍中將 191.75克之三甲基矽氧甲氧基_2_乙基丙烯添加至 13.75毫升1Μ之含於四氩呋喊(“TMF”)中之四丁基銨_間· 氣苯甲酸鹽(“TBACB”)溶液、30.0克雙(二甲基胺基)甲 基魏、6U9克對-二甲苯、154.28克甲基丙稀酸甲酿及 1892」3克含於4399·78克TMF中之2_(三甲基矽氧基)乙 基曱基丙烯酸酯中在經過260分鐘的期間添加3〇毫升額 外之含於響中之TBACB(G_4M),期間使反應混合物放 熱,然後冷卻至30°C。在添加2-(三甲基矽氧基)乙基甲 -12- 559588 A7 B7 五、發明說明(u) 基丙烯酸酯之後六十分鐘,添加含467.56克2_(三甲基石夕 氧基)乙基甲基丙烯酸醋、3636.6克mPDMS及3673.84 克TRIS和20.0克雙(二甲基胺基)甲基矽烷之溶液。使混 合物放熱,然後冷卻至30°C2小時。然後添加含ι〇·〇克 雙(二甲基胺基)甲基矽烷、154.26克甲基丙烯酸甲酯和 1892.13克2-(二甲基梦氧基)乙基曱基丙婦酸g旨之溶液並 再次使混凝土物放熱。於2小時後,添加2加侖之無水 THF,接著在使溶液冷卻至34°C之後,添加含439.69克 水、740.6克曱醇和8.8克二氣醋酸之溶液。迴流混合物 4·5小時,以油浴在ll〇°c下加熱,並在135°C下蒸餾掉 揮發物,添加甲苯以幫助去除水,直到達到11〇。〇之蒸氣 溫度為止。 使反應燒瓶冷卻至110°C,添加含443克二甲基間-異 丙烯苄基異腈酸酯和5.7克二月桂酸二丁錫之溶液。使混 合物反應3.5小時,然後冷卻至30°C。在減壓下蒸發甲 苯以產生偏白、無水、蠟質之反應性巨體。 經濟部智慧財產局員工消費合作社印製 矽氧烷水凝膠鏡片係利用具下述之具體的混合物來製造 :14重量百分比TRIS、26重量百分比DMA、28重量百 分比mPDMS ; 2重量百分比NORBLOC™ ; 1重量百分比 TEGDMA ; 5重量百分比HEMA ;及8重量百分比 PVP,併同小量之添加物及稀釋劑。以下程序被用來形成 鏡片。 隱形眼鏡係藉添加大約0.10克鏡片材料至TOPAS®模 穴及將材料固化大約1200秒來製造。聚合反應係在氮氣 •13· 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 559588 A7 B7 經濟部智慧財產局員工消費合作社印製 五、發明說明(12) 流下進行並以Andover股份有限公司之420PS10-25AM 39565-02濾光器所產生之5毫瓦平方公分紫外光予以光 引發。於固化完成後,開啟模具,並將鏡片釋出於1:1之 水和異丙醇之換合物中,並於異丙醇中瀝洗以去除殘餘之 單體及稀釋劑。將鏡片平衡於生理之硼酸鹽·緩衝之食鹽 水中。於45 °C下,藉浸潰經瀝洗之鏡片於1 ·〇 %含 250,000 MW聚(丙烯酸)於硼酸鹽-緩衝之食鹽水中之溶液 (其中添加0.1%之1-[3-(二甲基胺基)丙基]-3 -乙基碳化 二醯亞胺氫氣酸鹽)來塗覆鏡片。在攪拌大約30分鐘 後,於硼酸鹽-緩衝之食鹽水溶液中浸泡鏡片。 鏡片試驗 對所有鏡片測定活體外刀痕,係藉將每個鏡片吸乾並將 鏡片放在一鋼質、44.75D (7.55毫米半徑)之角膜弧度測 定儀之校正標準品上,利用一蔡司狹縫燈(型號3〇sl/m 具電力供應31 04 58),在最大照光下,以16_4加放大 來尋找刀痕的有或無。除了實施例1-18的鏡片外,實施 例19及20係試驗由lotrafilcone A (未塗覆及經塗覆)與 聚(丙烯酸)所製得之FOCUS® NIGHT & DAY每日配戴式 鏡片。下表列出此研究的結果。 -14- 適 度 尺 張 紙 本 標 家 格 規 )A4 釐 公 97Shaft speed. The insert of the present invention may be composed of any material that can be optically processed, including (non-limiting) metals, quartz, ceramics, polymers, and the like. Suitable metals include (non-limiting) pure steel, brass, copper, nickel-plated substrates, chrome, cobalt-alloyed steel, AMPCOLOY ™ substrates, and their combinations. Preferably, the insert is nickel-plated copper or nickel-plated brass. Examples of useful polymer materials include (non-limiting) polycarbonate, cyclodipene, nylon, DELRIN®, TEFLON®, polystyrene, polypropylene, poly (acrylonitrile), and the like, and combinations thereof. The insert is used to form the mold or mold half of the present invention using any conventional method. Usually, the mold is cast from an insert. Basically, inserts suitable for forming the molding surface of a mold or mold half should be paired with complementary inserts used to form the non-mold surface of the mold or mold half. The mold of the present invention can be made of any material suitable for use in the manufacture of contact lenses. Suitable mold materials include (non-limiting) polyolefins, such as polypropylene, polystyrene, cyclic polyolefins, polyacrylonitrile materials, and combinations thereof. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The mold and pieces of the present invention can be used to make any kind of broken-oxygen fired hydrogel lenses. The lens of the present invention is a silicone hydrogel, preferably the silicone hydrogel is coated with an expandable coating. Suitable silicone hydrogel materials include, but are not limited to, silicone hydrogels made from silicon giants, such as the pendant hydrophilicity described in U.S. Patent Nos. 43259,467, 4,260,725, and 4,261,875 Polydimethylsiloxane with methacrylate esterification; or described in U.S. Patent Nos. 4,136,250; 4,153,641; 4,189,546; 4,182,822; 4,343,927; 4,254,248; 4,355,147; 4,276,402; 4,327,203; 4,341,889 ; -6 · This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) 559588 Α7 Β7 V. Description of the invention (5) 4,486,577; 4,605,712; 4,543,398; 4,661,575; 4,703,097; 4,837,289; 4,954,586; 4,954,587 5,346,946; 5,358,995; 5,387,632; 5,4513617; 5,486,579; 5,962,548; 5,981,615; 5,981,675 and 6,039,913 polydimethylsiloxane macropolymers with polymerizable functionality. They can also be manufactured using polysiloxane macromonomers combined with hydrophilic monomers, such as those described in U.S. Patent Nos. 5,010,141; 5,057,578; 5,314,960; 5,371,147, and 5,336,797; or containing polydimethylsiloxane Giants of oxane blocks and polyether blocks, as described in U.S. Patent Nos. 4,871,785 and 5,034,461. The entire contents of the patent case are incorporated herein by reference. Suitable materials can also be made from a combination of oxyperm and ionoperm ingredients, such as described in U.S. Patent Nos. 5,760,100; 5,776,999; 5,789,461; 5,807,944; 5,965,631, and 5,958,440. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Hydrophilic Monomers for inclusion in these copolymers, including 2-hydroxyethyl methacrylate, fluorenyl ethyl acrylate ("HEMA"), N, N-dimethylpropanamine (DMA "), N-ethylene 0 biloxamine_, 2-ethylene · 4,4 '· dimethyl-2-jinsalyl-5-one, methacrylic acid, 2_Hydroxyethylmethacrylamide. Other siloxane monomers can be added, such as tris (trimethylsiloxy) silylpropylmethacrylate, or described in US Patent No. 5998 498; 3, 8〇8178; 4,139,513; 5,070,215; 5,710,302; 5,714,557, and 5,908,906. Siloxane monomers. They can also include various toughening agents, toners, νν blocking agents and wetting agents. They can be diluted Agents, such as those described in U.S. Patent No. 6,020,445 for primary or secondary alcohols or tertiary alcohols. The entire contents of the patent case are incorporated herein by reference. In the preferred embodiment, the lens of the present invention —Species of giants and Bao-7- 559588 A7 B7 V. Description of the invention (6) Monomer and hydrophilic monomer-based siloxane reaction mixture It can be made by the reaction. The giant can be made by combining a methacrylate or an acrylate with a siloxane in the presence of a group transfer polymerization ("GTP") catalyst. These giants are basically various Copolymers of monomers. Their formation can be in the form of distinct blocks of monomers or aggregated in a generally random distribution. These giants can further be linear, branched, or star-shaped. The formation of branched structures such as polymethyl Acrylates or cross-linkable monomers (such as 3- (trimethyl dreamoxy) propyl methacrylate) are included in the macro. Initiators, reaction conditions, Monomers and catalysts are described in "Groups_Transfer Polymerization" described by OW · Webster, printed by John Wiley & Sons, Consumer Cooperatives of the Intellectual Property Bureau, Ministry of Economics, Polymer Science and Engineering, Encyclopedia of Economics. In the "method", these polymerization reactions are performed under anhydrous conditions. Via functional monomers (such as HEMA) can be mixed into their trimethyl dream oxyesters, which are hydrolyzed to form free hydroxyl groups after polymerization. GTP provides Aggregation control molecule Quantity distribution and the ability of the monomers on the chain to disperse the macromolecules. Then this giant can be combined with polydimethylsiloxane (preferably monomethacryloxypropyl terminated polydimethylsiloxane) A reaction mixture of siloxane ("mPDMS") and a hydrophilic monomer. The preferred mPDMS is the formula: ^ 59 59 〒59 ^ 58-Si-O- ^ · Si-Si-1 ^ 〇R59 R59 R59 where b = G to ⑽, preferably 8 to 1G; R58 is a monovalent group 81 containing ethyl unsaturation, preferably containing phenylethyl, fluorenyl, or methacrylic acid, and most preferably methyl Monovalent group of the acrylate group part. Each R59 is independently a monovalent alkyl group or an aryl group, which can be further subjected to alcohol, amine, -8-559588 A7 B7. 5. Description of the invention (7) _, carboxylic acid or ether group Substituted, preferably an unsubstituted monovalent alkyl or aryl group, particularly preferably a methyl group; and Chi 60 is a monovalent alkyl group or an aryl group, which may be further subjected to alcohol, amine, ketone, carboxylic acid or ether It is preferably an unsubstituted monovalent alkyl or aryl group, preferably a C ^ o aliphatic or aromatic group (which may include a hetero atom), particularly preferably a C3_8 alkyl group, and most preferably butyl Special Is the second butyl. Members of the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives have printed better macro ingredients including mPDMS, 3-methacryloxypropyl tris (trimethylsiloxy) silane ("TRIS"), methyl methacrylate, HEMA , DMA, methacrylonitrile, ethyl methacrylate, butyl methacrylate, 2-hydroxypropyl-1-fluorenyl acrylate, 2-hydroxyethyl methacrylate, and methacrylic acid. Even better, the giant system is made from a reaction mixture of HEMA, methyl methacrylate, TRIS, and mPDMS. In the best case, the giant system consists of, substantially contains, or contains about 19.1 moles of HEMA, about 2.8 moles of methyl methacrylate, about 7.9 moles of TRIS, and about 3.3 moles of monomethacrylic acid. An oxypropyl-terminated monobutyl-terminated polydimethylsiloxane reaction mixture is prepared by combining the above materials with 3-isopropenyl-ω, ω -The dimethyl benzyl isocyanate reaction is completed using dibutyltin dilaurate as a catalyst. The reaction component of the silicone hydrogel is basically a combination of a hydrophobic silicone and an extremely hydrophilic component. Because these ingredients are usually not miscible due to their polar differences, it is particularly advantageous to combine a combination of a hydrophobic siloxane and a hydrophilic monomer (especially those with hydroxyl groups) into a giant. This giant was then used to mix with the others in the final reaction mixture. -9- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) A7 B7 559588 5. Description of the invention (0 Siloxane and hydrophilic The monomers are compatible. These blends typically also include a diluent to further compatibility and dissolve all the ingredients. Preferably, the hydrogel based on Shixian sintering is prepared by reacting the following monomer mixture Formation: giant; si7-9 monomethacryloxy-terminated polydimethylsiloxane; and hydrophilic monomers with small amounts of additives and photoinitiators. Particularly preferably, the hydrogel is borrowed Made by reacting the following monomers: Si7_9 monomethacryloxy-terminated polydimethylsiloxane; TRIS; DMA; HEMA and tetraethylene glycol dimethacrylate ("TEGDMA"). Optimally , Hydrogel is made of giant (about 18%); Si7_9 monomethacryloxy-terminated polydimethylsiloxane (about 28%); DMA (about 26%); HEMA (about 5%) TEGDMA (about 1%); polyvinylpyrrolidone ("PVP") (about 5%) and the balance containing small amounts of additives and photoinitiators • Amounts (all amounts are based on the composition Calculated by weight percent of total weight), the reaction is carried out in the presence of 20% by weight of dimethyl-3 · octanol diluent. The surface of contact lenses printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs An expandable coating can be applied by any convenient method such as applying a suitable hydrophilic coating. This coating can be applied by any convenient method. Preferred hydrophilic coatings include (non-limiting) poly (acrylic), poly (Methacrylic acid), poly (maleic acid), poly (itaconic acid), poly (acrylamide), poly (monomethacrylamide), (meth) propionic acid, acrylic Acids, (maleic acid, itaconic acid and any reactive ethylene monomer, carboxymethylated polymers such as carboxymethyl cellulose, dextrin, polyvinyl alcohol, polyethylene oxide, poly ( HEMA), polysulfonate, polysulfate, polylactam, polyglycolic acid, polyamine, etc. and mixtures thereof, block or random copolymers. Particularly preferably, the coating is poly (acrylic), poly ( Methacrylic acid), poly-10-559588 A7 B7 5. Description of the invention (9 ) Methacrylamide, poly (acrylamide) or poly (HEMA). The best use is poly (acrylic acid), poly (acrylamide) or poly (HEMA). The lens of the present invention can use any Conventional methods for the manufacture of contact lenses. Preferably, the lenses are made by photo-curing the lens composition and applying a layer of coating to the cured lens. In contact lens manufacturing, various known reaction mixtures are available for molding. The method includes spin casting and static casting. The preferred method for manufacturing the contact lens of the present invention is a direct molding method using a siloxane hydrogel, which is economical and can precisely control the final shape of the hydrated lens. For this method, 'the reaction mixture is placed in a mold having the shape of the final desired hydroxane hydrogel (ie, a water-swellable polymer), and the reaction mixture is subjected to conditions under which the monomers can be polymerized to produce a final Polymer of approximate shape of the desired product. The conditions for such polymerization are well known in the art. The polymer mixture may optionally be treated with a solvent and then treated with water to produce a stone-oxygen fired hydrogel having a final size and shape similar to the original molded polymer article. This method can be used to form contact lenses and this method is further described in U.S. Patent Nos. 4,495,313, 4,680,33, 4,889,664, and 5,039,459 (all of which are incorporated herein by reference). Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economics The present invention will be further clarified by considering the following non-limiting examples. Examples 1-18 Inserts and Molds Manufacture Inserts are turned by brass with a diamond tip -11- This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) ^ ----- 559588 A7 B7 V. Description of the invention (10) Manufacturing. Unless otherwise specified, all brass inserts are cut with 4 semi-finished cuts, cutting depth = 0.25 mm, spindle speed 8,000 rpm and feed rate 25 mm / min. Then cut the insert with a cutting depth = 0.005 mm, a spindle speed of 8,000 rpm and a feed rate of 5 mm / min. The insert is then: 1.) untreated; 2.) treated with a thin nickel coating of about 2-4 microns, which is applied to the surface of the insert by evaporation; 3 ·) treated with a thin nickel coating of about 100-200 microns , Coated on the surface of the insert by evaporation; or 4 ·) polished with diamond polishing paste. In Example 1-18, the lens mold half mold was injection molded from TOP AS polymer using the inserts listed in the table below. The parts are installed in an 8-hole injection molding machine and the molten TOPAS® is injected into the mold under pressure at about 290-300 ° C. Relieve the pressure, allow the mold to cool, open and eject the mold. Lens Formation-Example M8 The giant system used for printing and manufacturing lenses for employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs was used to add 141.7 tons of trimethylsilyloxy-2-ethylpropene in a nitrogen atmosphere. To 13.75 ml of 1M tetrabutylammonium-m-gas benzoate ("TBACB") solution in tetrahydrofuran ("TMF"), 30.0 g of bis (dimethylamino) methylwei , 6U9 grams of p-xylene, 154.28 grams of methyl acrylic acid and 1892 "3 grams of 2- (trimethylsiloxy) ethylfluorenyl acrylate contained in 4399 · 78 grams of TMF. During the minutes, 30 ml of additional TBAPB (G_4M) contained in the ring was added, during which the reaction mixture was exothermic and then cooled to 30 ° C. Sixty minutes after adding 2- (trimethylsiloxy) ethylmethyl-12-559588 A7 B7 5. Description of the invention (u) acrylate, add 467.56 g of 2- (trimethylsiloxy) ethyl A solution of methacrylic acid vinegar, 3636.6 grams of mPDMS and 3673.84 grams of TRIS and 20.0 grams of bis (dimethylamino) methylsilane. The mixture was allowed to exotherm and then cooled to 30 ° C for 2 hours. Then add ιο. G of bis (dimethylamino) methylsilane, 154.26 g of methyl methacrylate, and 1892.13 g of 2- (dimethyldreamoxy) ethylfluorenylpropionic acid g Solution and heat the concrete again. After 2 hours, 2 gallons of anhydrous THF was added, and after the solution was cooled to 34 ° C, a solution containing 439.69 g of water, 740.6 g of methanol, and 8.8 g of diacetic acid was added. The mixture was refluxed for 4.5 hours, heated in an oil bath at 110 ° C, and the volatiles were distilled off at 135 ° C. Toluene was added to help remove water until it reached 11 °. 〇The steam temperature so far. The reaction flask was cooled to 110 ° C, and a solution containing 443 g of dimethyl m-isopropenyl benzyl isocyanate and 5.7 g of dibutyltin dilaurate was added. The mixture was reacted for 3.5 hours and then cooled to 30 ° C. Toluene is evaporated under reduced pressure to produce a pale, anhydrous, waxy reactive macrosome. Siloxane hydrogel lenses printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs are manufactured using the following specific mixtures: 14 weight percent TRIS, 26 weight percent DMA, 28 weight percent mPDMS; 2 weight percent NORBLOC ™; 1 weight percent TEGDMA; 5 weight percent HEMA; and 8 weight percent PVP, with the same small amount of additives and diluent. The following procedure was used to form the lens. Contact lenses are manufactured by adding approximately 0.10 grams of lens material to the TOPAS® cavity and curing the material for approximately 1200 seconds. The polymerization was carried out under nitrogen • 13. This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 559588 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) The 5 mWcm UV light generated by Andover Co., Ltd.'s 420PS10-25AM 39565-02 filter was used for photoinitiation. After curing is completed, the mold is opened, and the lens is released into a 1: 1 water and isopropanol exchange mixture, and is leached in isopropanol to remove residual monomer and diluent. The lenses were equilibrated in physiological borate · buffered saline water. Leach the leached lens at 45 ° C in a 1.0% solution containing 250,000 MW poly (acrylic acid) in borate-buffered saline (with the addition of 0.1% 1- [3- (dimethylformate) Aminoamine) propyl] -3-ethylcarbodiimide hydrochloride) to coat lenses. After stirring for about 30 minutes, soak the lenses in a borate-buffered saline solution. The lens test measures in vitro knife marks on all lenses by absorbing each lens dry and placing the lens on a steel, 44.75D (7.55 mm radius) corneal radian tester calibration standard using a Zeiss Narrow The sewing lamp (model 30sl / m with power supply 31 04 58), under the maximum light, use 16_4 magnification to find the presence or absence of knife marks. In addition to the lenses of Examples 1-18, Examples 19 and 20 were tested on FOCUS® NIGHT & DAY daily lenses made from lotrafilcone A (uncoated and coated) and poly (acrylic) . The following table lists the results of this study. -14- Appropriate rule for paper rulers) A4 cm 97
559588 A7 B7 五、發明說明(ι〇 經濟部智慧財產局員工消費合作社印製 實施例 鏡片曲率(D) 鼓件/鏡片 鏡片刀痕/分 光作用率 1 -4.00 拋光黃銅/PAA塗覆 0%(0/5) 2 -2.50 未拋光黃銅/PAA塗覆 60%(3/5) 3 -2.50 拋光黃銅/PAA塗覆 0%(0/5) 4 -2.00 未拋光黃銅/PAA塗覆 100%(5/5) 5 -2.00 拋光黃銅/PAA塗覆 0%(0/5) 6 -2.50 未拋光黃銅/PAA塗覆 60%(3/5) 7 -2.50 拋光黃銅/PAA塗覆 0%(0/5) 8 -4.00 未拋光黃銅/PAA塗覆 100%(5/5) 9 -2.50 薄NI塗覆之黃銅/PAA塗覆 100%(5/5) 10 -4.00 薄NI塗覆之黃銅/PAA塗覆 100%(5/5) 11 -2.50 厚NI塗覆之黃銅/PAA塗覆 100%(10/10) 12 -4.00 厚NI塗覆之黃銅/PAA塗覆 14%(1/7) 13 -2.50 拋光黃銅/PAA塗覆 100%(10/10) 14 -4.00 拋光黃銅/PAA塗覆 0%(0/10) 15 -4.00 未拋光黃銅 刀具進給速度7.5毫米/分鐘 @5000 rpm/未塗覆 0%(0/5) 16 -4.00 未抛光黃銅 刀具進給速度7.5毫米/分鐘 @5000 rpm/PAA 塗覆 100%(10/10) 17 -4.00 未拋光黃銅 刀具進給速度5毫米/分鐘 @8000 rpm/未塗覆 0%(0/5) 18 -4.00 未拋光黃銅 刀具進給速度5毫米/分鐘 @8000 rpm/PAA 塗覆 100%(10/10) 19 -1.00 未塗覆 0%(0/2) 20 -1.00 PAA塗覆 50%(1/2) -15- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)559588 A7 B7 V. Description of the invention (ι〇 Example printed by employees of the Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Cooperatives, Lens Curvature (D) Drum / Lens Lens Cut / Spectral Action Rate 1 -4.00 Polished brass / PAA coating 0% (0/5) 2 -2.50 unpolished brass / PAA coated 60% (3/5) 3 -2.50 polished brass / PAA coated 0% (0/5) 4 -2.00 unpolished brass / PAA coated 100% (5/5) 5 -2.00 Polished brass / PAA coated 0% (0/5) 6 -2.50 Unpolished brass / PAA coated 60% (3/5) 7 -2.50 Polished brass / PAA coated 0% (0/5) 8 -4.00 Unpolished brass / PAA coated 100% (5/5) 9 -2.50 Thin NI coated brass / PAA coated 100% (5/5) 10 -4.00 thin NI coated brass / PAA coated 100% (5/5) 11 -2.50 thick NI coated brass / PAA coated 100% (10/10) 12 -4.00 thick NI coated yellow Copper / PAA coated 14% (1/7) 13 -2.50 Polished brass / PAA coated 100% (10/10) 14 -4.00 Polished brass / PAA coated 0% (0/10) 15 -4.00 Not Feed rate of polished brass tool 7.5 mm / min @ 5000 rpm / 0% uncoated (0/5) 16 -4.00 Feed rate of polished brass tool 7.5 mm / min @ 5000 rpm / PAA coated 100% ( 10/10) 17 -4.00 unpolished yellow Tool feed rate 5 mm / min @ 8000 rpm / 0% uncoated (0/5) 18 -4.00 Unpolished brass tool feed rate 5 mm / min @ 8000 rpm / PAA coated 100% (10/10 ) 19 -1.00 Uncoated 0% (0/2) 20 -1.00 PAA coated 50% (1/2) -15- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)